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Volumn 34, Issue 7, 1995, Pages 713-745

Calixarenes, Macrocycles with (Almost) Unlimited Possibilities

Author keywords

calixarenes; host guest compounds; metacyclophanes; resorcarenes; supramolecular chemistry

Indexed keywords


EID: 33748539998     PISSN: 05700833     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.199507131     Document Type: Review
Times cited : (2236)

References (646)
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    • (a) An exact molecular weight determination was difficult and several “tetramers” were later shown to be octamers.
  • 4
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    • (b) An excellent description of the development of calixarene chemistry can be found in ref. [1]. Together with [2] this provides details of all the important developments up to the end of the 1980s. For a special acknowledgement of the earliest developments see
    • (1992) Oesterr. Chem. Ztg. , vol.93 , pp. 28-31
    • Kappe, T.1
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    • (a) See also the recent review of some aspects of the chemistry of calixarenes derived from phenol
    • (1993) Tetrahedron , vol.49 , pp. 8933-8968
    • Shinkai, S.1
  • 9
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    • (b) Because of the variety of possibilities they offer, calixarenes are described there (incomparison with crown ethers and cryptands) as “supramolecules of the third generation”
  • 57
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    • (b) The azulene analogue of a calix[4]arene tetramethyl ether has also been obtained by 2 + 2 condensation, see ref. [58].
  • 64
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    • We recently obtained calix[6]arenes, including examples with OH groups in exo position in a “4 + 2” condensation, cf. ref. [38].
  • 70
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    • (b) The sterically more demanding tert‐butyl groups favor an intramolecular hydrogen bond more than do methyl groups.
  • 77
    • 84985543398 scopus 로고    scopus 로고
    • This defines the orientation of the group R with respect to one of the CHR bridges. If the macrocyclic system is viewed as being planar, these groups are either on the same side (c) or on the opposite side (t) to the group taken as a reference (r). However, this classification is not always used. Gutsche uses the cis/trans notation to denote the relative orientation of two neighboring bridges (cf. [1]). Thus he describes the rtct isomer as the trans,trans,trans,trans isomer. Further confusion is caused by the fact that these configurational isomers can (at least in principle) adopt different conformations, and that these two stereochemical aspects are not always clearly distinguished.
  • 86
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    • (e) for the application of other aldehydes see ref. [185a].
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    • (e) The structures of cyclic tetramers in which chromotropic acid units are linked by methylene bridges, appear, in view of the given data, not to be confirmed unequivocally
    • (1993) Tetrahedron , vol.49 , pp. 3489-3856
    • Poh, B.‐P.1    Tan, C.M.2    Loh, C.L.3
  • 118
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    • (a) This has already been formulated in principle by Cornforth (cf. ref. [1]), although he considered these conformers to be separable isomers.
  • 119
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    • (b) A description suggested recently by Gutsche et al. for calix[6]arenes (cf. ref. [92]) could also be applied to other calixarenes.
  • 120
    • 84985573336 scopus 로고    scopus 로고
    • Conformations of Calixarenes in the Crystalline State in ref. [2], p. 65–85
    • Perrin, M.1    Oehler, D.2
  • 121
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    • Inclusion Properties and Host‐Guest Interactions of Calixarenes in the Solid State in ref. [2], p. 87–123. For more recent examples see ref. [167a, 278a] and
    • Andreetti, G.D.1    Ugozzoli, F.2
  • 127
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    • Shinkai et al. report that p‐hexanoylcalix[4]arene crystallizes out in the partial cone conformation from the melt at higher temperatures (see ref. [162]).
  • 139
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    • 5 symmetry see ref. [83].
  • 144
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    • (e) see also ref. [18b].
  • 149
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    • Since the aromatic systems (including the atoms bonded to them) can be considered to be planar even as a very good approximation, a calix[n]arene can in principle be described by (n‐1) pairs of such torsional angles. However, n pairs are given for the sake of clarity. The cone conformation (and any cone‐like conformation) is characterized by a continual change of sign (+ –) within these pairs. The other conformations of calix[4]arenes are described as follows: partial cone + –, + –, + +, –; 1,2‐ alternate + –, + +, – +, –, and 1,3‐ alternate + +, ‐, + +, –. The conformations of calix[6]arenes (Fig. 2) have torsional angles with the following sign sequences: left + –, + –, – +, + –, + –, – +; right + –, + –, +, – +, – +, –.
  • 160
    • 84985536899 scopus 로고    scopus 로고
    • Most of the structures refer to derivatives such as the octaesters (Section 5.2), cavitands, carcerands etc. (Section 6.2) and thus also naturally prove the structure of the parent calix[4]arenes.
  • 171
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    • Single Step Synthesis and Properties of Calixarenes, in ref. [2], p. 3–37.
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    • s symmetry, which has also been described as the diamond conformation (see ref. [45a]).
  • 176
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    • 6]dimethyl sulfoxide, are assigned to diffrent OH groups in systems of cyclic hydrogen bonds, see ref. [274].
  • 181
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    • Melting point differences of up to 180 °C can be caused merely by different sequences of the phenol units in positional isomers of calix[4]arenes of the type ABCD, see ref. [29b].
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    • A slow isomerization of the tetra‐O‐alkyl derivatives has been observed for ethyl groups (, Chem. Lett.) and even for β‐hydroxyethyl groups (footnote in ref. [285a])
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    • Araki, K.1    Iwamoto, K.2    Shinkai, S.3    Matsuda, T.4
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    • While a numbering of all the C atoms based on the IUPAC name is also used, so that for example the 1,3‐dimethyl ether of a calix[4]arene is to be named as 25,27‐dihydroxy‐26,28‐dimethoxycalix[4]arene (see ref. [1]), this inconsequence appears to cause no confusion in practice.
  • 253
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    • (c) in the case of 1,2‐O‐alkylation with 2‐chloromethylpyridine a yield of 85% was recently reported [222b].
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    • A structure, in which the opposing phenol units are really coplanar, would lead on the basis of standard bond lengths to an unusually short OO distance and should therefore not correspond to an energy minimum.
  • 295
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    • (c) for aminomethylation see also ref. [170].
  • 300
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    • Water Soluble Calixarene Salts. A Class of Compounds with Solid‐State Structures Resembling Those of Clays, in ref. [2], p. 199–210.
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    • (c) cf. also the calix‐salophene crowns in ref. [271].
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    • (c) see also ref. [283].
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    • Calixarenes in which two neighboring p‐positions are bridged (compare ref. [37b]) have been described by, J. Chem. Soc. Perkin Trans. 1
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  • 379
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    • (c) compare also [156b]. For the linkage of two calix[4]arenes functionalized in p‐position by four bridges (compare ref. [41b]) see
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    • (a) Otherwise a complex mixture of isomeric or similar derivatives would be formed. Thus for example four different mono‐ or trialkyl derivatives (with a syn arrangement) or four different tetraalkyl derivatives in the cone conformation are possible
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    • Unfortunately a recent systematic classification (cf. ref. [221]) of all possibilities contains some mistakes and inconsistencies. The number of different O‐alkylation products (in brackets the number of the chiral compounds) is as follows: 34 (17) tetra‐, 13 (9) tri‐, 8 (3) dialkyl ethers. Compare
    • (1994) Supramol. Chem. , vol.3 , pp. 229-301
    • Böhmer, V.1    Kraft, D.2    Vogt, W.3
  • 421
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    • Mono‐ and tri‐O‐alkyl derivatives of calix[4]arenes of the type AABB have also no plane of symmetry, and analogous considerations apply to macrocycles such as 2 or 5 with a “non‐quadratic” arrangement of the phenolic oxygen atoms; see ref. [23b].
  • 429
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    • This demonstrates best that the transitions between calixarenes in the narrow sense (Type II) and the resorcarenes (Type III) are gradual. For other calix[4]arenes with resorcinol units, which are bonded through the 2,6‐positions, see ref. [32c].
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    • 2; see ref. [323c].
  • 445
    • 84985612493 scopus 로고    scopus 로고
    • Since this highly aesthetic structure is one of the most often reproduced representations of calixarenes we shall not include it here.
  • 449
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    • (a) The conformational change of the O‐alkyl groups can also be used in order to align them for an interaction with a further guest:, J. Chem. Soc. Chem. Commun.
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    • III comples of calixarene sulfonates also exhibit luminescence in aqueous solution:, Chem. Lett., 1261–1264.
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    • +, see ref. [325c]
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    • (b) similar observations have been made for tetra‐O‐alkyl derivatives in the 1,3‐alternate conformation:, Tetrahedron Lett.
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    • (a) The replacement of the ethyl ester residues in 62 by methoxy groups leads to compounds whose fluorescence spectra depend on the polarity of the solvent:, J. Chem. Soc. Chem. Commun.
    • (1991) , pp. 1771-1773
    • Aoki, I.1    Kawabata, H.2    Nakashima, K.3    Shinkai, S.4
  • 514
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    • (e) for the electrochemical detection of ammonium ions see ref. [174b].
  • 515
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    • (a) See ref. [168]; the effect can only with difficulty be reconciled with the calixarene structure, as podands with analogous ferrocenecarbonamide structures show even greater effects.
  • 538
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    • Supramolekulare Komplexe von Calix[4]arenen mit beweglichem erweitertem Hohlraum - Struktur einer molekularen Venusfliegenfalle
    • (a) For an example with a variable cavity “molecular Venus flytrap” see
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    • Atwood, J.L.1    Orr, G.W.2    Bott, S.G.3    Robinson, K.D.4
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    • 18. Int. Symp. Macrocycl. Chem., 27. June—2. July 1993, Enschede, The Netherlands.
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    • (b) The alkaline hydrolysis of monobenzoates of tert‐butylcalix[4]arene in ethanol/water is accelerated by a factor of up to 160 with respect to model compounds:, J. Chem. Soc. Perkin Trans. 2, 83–88.
    • (1994)
    • Ray, K.B.1    Weatherhead, R.H.2    Pirinccioglu, N.3    Williams, A.4
  • 586
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    • In the period from December 1993 to November 1994 about 200 publications dealing with calixarenes and resorcarenes were published.
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    • (c) for the acylation of p‐cyanomethylcalix[4]‐arene see:, Synthesis, 813
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    • Sharma, S.K.1    Gutsche, C.D.2
  • 619
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    • (e) the same authors propose a structure, which is sterically more probable, however the fourfold intramolecular bridging by bis‐diazonium salts remains unlikely:, J. Chem. Soc. Chem. Commun.
    • (1994) , pp. 2593-2594
    • Chawla, H.M.1    Srinivas, K.2
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    • + selectivity based on calix[4]‐crown‐4 see:, Chem. Lett., 1115
    • (1994) , pp. 1118
    • Yamamoto, H.1    Shinkai, S.2
  • 641
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    • (b) a second slightly later publication reprots the achievement of 99.8% purity using an amazingly identical procedure:, Chem. Lett., 699–702.
    • (1994)
    • Suzuki, T.1    Nakashima, K.2    Shinkai, S.3


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